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JCJ 8928 



Bureau of Mines Information Circular/1983 



.; 2'c1983 






Chemical Vapor Deposition of Group IVB, 
VB, and VIB Elements With Nonmetals 



A Literature Review 



By H. O. McDonald and J. B. Stephenson 




UNITED STATES DEPARTMENT OF THE INTERIOR 



■j^faf &*ti^- &sx>^- ~j p^ 



Information Circular 8928 

\ 



Chemical Vapor Deposition of Group IVB, 
VB, and VIB Elements With Nonmetals 



A Literature Review 



By H. O. McDonald and J. B. Stephenson 




UNITED STATES DEPARTMENT OF THE INTERIOR 
James G. Watt, Secretary 

BUREAU OF MINES 
Robert C. Horton, Director 



^z°t> 









# 



This publication has been cataloged as follows: 



McDonald, H, 4 (Hector 0.) 








Chemical vapor deposition of group IVB, 


VB, 


and VIB elements with 


nonmetals: a literature review. 








(Information circular / Bureau of Mines : 


8928) 






Bibliography: p. ]4-29. 








Supt. of Docs, no.: I 28.27:8928. 








1. Vapor-plating. I. Stephenson, J. B. (J 


ames 


Blake), 1942- 


ll. 


Title. 111. Series: Information' circular 


'United States. Bureau 


of 


Mines) ; 8928. 








TN295.U4 [TS695] 622s [671, 7'35 


1 


83-600000 






CONTENTS 



Page 



■to VAbstract 1 

Introduction 2 

Group IVB metals (Ti, Zr, Hf) 2 

Titanium boride 2 

Zirconium boride 3 

Titanium carbide 3 

Zirconium carbide 5 

Hafnium carbide 5 

Titanium carbonitride 5 

Titanium nitride 6 

K Zirconium and haf nium nitrides 7 

Miscellaneous compounds 7 

oup VB metals [V, Nb(Cb), Ta] 9 

Miscellaneous vanadium compounds 9 

Niobium and tantalum borides 9 

Niobium and tantalum carbides 9 

Niobium and tantalum nitrides 9 

Miscellaneous compounds 10 

Group VIB metals (Cr, Mo, W) *. 10 

Chromium carbide 10 

Molybdenum carbide 11 

Tungsten carbide 12 

Molybdenum and tungsten borides and silicides 12 

Conclusions 13 

References 14 

TABLES 

1 . Some CVD reactions for group IVB elements 8 

2. Some CVD reactions for group VB elements 11 

3. Some CVD reactions for group VIB elements 13 




- 





UNIT OF MEASURE 


ABBREVIATIONS USED 


IN. THIS REPORT 


atm 


atmosphere 






min 


minute 


° C 


degree Celsius 






mL 


milliliter 


cm 


centimeter 






mm 


millimeter 


eV 


electron volt 






urn 


micrometer 


hr 


hour 






mole 


gram mole of material 


Hz 


hertz, reciprocal 


s 


econd 


pet 


percent 


kcal 


kilocalorie 






sec 


second 


kg 


kilogram 






torr 


millimeter of Hg pressure 


mA 


milliampere 











CHEMICAL VAPOR DEPOSITION OF GROUP IVB, VB, 
AND VIB ELEMENTS WITH NONMETALS 

A Literature Review 

By H. 0, McDonald ' and J. B. Stephenson 2 



ABSTRACT 

The Bureau of Mines reviewed the chemical vapor deposition (CVD) lit- 
erature on the nonmetal binary and ternary compounds of the group IVB, 
VB, and VIB elements, with emphasis directed to the following nonmetals: 
B, C, N, 0, and Si. This review examines each of these binary and se- 
lected ternary compounds of the group IVB, VB, and VIB elements as coat- 
ings and gives some of their preparative methods, uses, and properties. 
A total of 259 references were found for these compounds of the nine 
elements. This review was utilized in the Bureau's research to provide 
abrasion-, erosion-, and corrosion-resistant coatings in order to con- 
serve critical metals and protect various metallic surfaces in metallur- 
gical, mining, and energy conversion systems. 

1 Research chemist, Rolla Research Center, Bureau of Mines, Rolla, Mo.; associate 
professor of chemistry, University of Missouri — Rolla, Rolla, Mo. 

^Research chemist, Rolla Research Center, Bureau of Mines, Rolla, Mo. 



INTRODUCTION 



Chemical vapor deposition (CVD) can be 
defined as a system in which one or more 
gaseous substances react on a heated sub- 
strate to form a compound or an element. 
CVD coatings have assumed a vital role in 
expanding the horizons of materials con- 
servation; CVD coatings have a signifi- 
cant influence on material properties, 
providing improved corrosion resistance, 
electrical contact resistance, reflectiv- 
ity, color, abrasion resistance, erosion 
resistance, and solderability , or a de- 
crease in the coefficient of friction. 
Preparation of semiconductor and super- 
conductor materials relies heavily on CVD 
technology. Using CVD coatings can re- 
duce the use of critical and strategic 
materials — while retaining improvements 
in desired material performance — in a 
wide variety of applications. 

CVD research by the Bureau of Mines 
has been conducted to minimize the 
consumption of strategic and critical 
materials in the manufacture of erosion-, 
abrasion-, and corrosion-resistant com- 
ponents used in metallurgical, mining, 
and energy conversion systems. Test re- 
sults were recently reported for one CVD- 
coated ball valve seat prepared during 
previous Bureau research ( 205 ) . 3 

The Bureau, a pioneer in the prepara- 
tion of CVD tungsten, is reviewing the 
literature relating to the deposition 
of abrasion-, erosion-, and corrosion- 
resistant coatings of the group IVB, 
VB, and VIB elements and compounds. A 



literature review of the group IVB, VB, 
and VIB elements was published in 1979 
( 133 ) . This present review brings to- 
gether many of the references that have 
appeared since about 1966 on the binary 
and selected ternary compounds of the 
group IVB, VB, and VIB elements with B, 
C, N, 0, and Si. 

Several CVD reviews have been pub- 
lished that give some of the deposition 
techniques, as well as the properties of 
the deposited metals and some of the 
binary compounds. One such article, 
by Archer (_5 ) , concerns a few metals 
and some metalloids. Broszeit and Ga- 
briel (31) have reviewed CVD techniques 
for protective coating and treatment for 
tools and structural parts. Perry and 
Archer ( 162-163 ) have surveyed wear- 
resistant coatings and some techniques of 
CVD. Yee ( 258 ) has made quite an exten- 
sive review of the use of CVD for pro- 
tective coatings. 

In addition to the review articles, 
there have been eight international con- 
ferences on CVD (21_-23, 42, 61_, _197, 203 , 
252 ) , which will not be covered in gen- 
eral here. 

In this review, the CVD literature will 
be considered for each group IVB, VB, 
and VIB metal, by periodic family, fol- 
lowed in each section by discussion 
of some of the methods of preparation, 
uses, and properties of the nonmetal 
deposits. 



GROUP IVB METALS (Ti, Zr, Hf) 



TITANIUM BORIDE 

Titanium diboride (TiB 2 ) is usually de- 
posited by the reaction of TiCl4 with 
BCI3 and H 2 at temperatures varying from 
850° to 1,400° C and near 1 atm total 
pressure ( 130 , 167 , 225 ) . Pierson and 
Randich have shown that TiB2 can be de- 
posited on Ta and stainless steels at 

^Underlined numbers in parentheses re- 
fer to items in the list of references at 
the end of this report. 



temperatures of 850° to 1,100° C, yield- 
ing surfaces with good erosion resistance 
and Knoop hardness of about 3,300 kg mm -2 
( 175 ). Takahashi, Sugiyama, and Suzuki 
grew TiB 2 fibers using a gas mixture of 
TiCl 4 , BCI3, H 2 , and Ar in an alternating 
current (ac) discharge ( 232 ) . Under 
these conditions, the reaction could be 
accomplished at the lower temperatures of 
300° to 700° C. Maximum growth was ob- 
tained at 400° C and discharge currents 
of 0.4 to 0.6 mA. Other investigators 
studied the growth of TiB 2 whiskers on 
quartz (146). They found that if small 



amounts of Au, Pt, or Pd were painted 
onto the substrates, the whisker growth 
was improved. Some single crystals of 
TiB 2 grown on Ta wire were demonstra- 
ted ( 212 ); however, the addition of HC1 
was essential, as well as temperatures of 
1,700° to 1,900° C. Several investi- 
gators studied the formation of TiB 2 on 
graphite substrates (1_8, 178-179 , 237 ). 

Besmann and Spear have published ther- 
modynamic ( 16 ) and kinetic (17) studies 
of the CVD of TiB 2 . Their results indi- 
cated that TiCl 3 , as well as HBC1 2 and 
HC1, was also present (16). They ob- 
tained a simple linear rate expression 
that was used to calculate an activation 
energy of 40±12 kcal mole -1 ( 15 , 17 ) for 
the deposition. Randich and Gerlach 
have published a method for calculating 
the phase diagram for the Ti-B-Cl-H 
system ( 188-189 ). 

Pierson and Randich ( 176-177 ) investi- 
gated the interaction of TiB 2 with the 
substrate. They found the substrate 
should not be deformed or transformed at 
temperatures up to 1,100° C, nor should 
it react with the byproducts of the reac- 
tion, in particular HC1. There was in 
some cases a thermal expansion difference 
that had to be corrected by the use of an 
interlayer of Ni or Cu. The substrates 
that could be used were Mo, W, Ta, Kovar, 
and high-Cr steels, as well as WC and 
TiC. These investigators found that a 
boride interlayer, usually M 3 B or M 2 B, 
was formed, possibly by diffusion. Here 
M could be a pure metal or an alloy. 
Ultrasound was employed to prepare thick 
films of TiB 2 on low carbon steel ( 220 ) . 
Pierson and Mullendore have reported the 
preparation of TiB 2 using B 2 H 6 instead of 
BCI3 ( 174 ) . Dense and adherent coatings 
were obtained using B 2 H 6 with TiCl 4 
and H 2 at 600° to 900° C on graphite 
substrates. 

Bonetti, Comte, and Hintermann (28) 
used metal borohydride compounds to 
boronize metals. In this process, 
Ti(BH 4 ) 5 was produced in situ by the re- 
action of TiCl4 with LiBH 4 in an air-free 
system at low temperatures. The thermal 
decomposition of Ti(BH 4 ) 3 at tempera- 
tures of 300° to 500° C yielded yellow 



metallic deposits, which were not found 
to be suitable at the present stage of 
this technology (28) . 

Good wear-resistant coatings of tita- 
nium boronitride (TiB 2 + x N y ) have recently 
been reported ( 170-171 ) . These coat- 
ings were produced by the action of 
TiCl 4 and BC1 3 with N 2 and H 2 at 1,150° 
to 1,450° C and pressures of 10 to 
20 torr ( 171 ). The cubic boronitrides 
with an atomic ratio B/(B + N) of less 
than 0.75 had microhardness values up to 
2,600 kg mm" 2 (170). 

ZIRCONIUM BORIDE 

Whiskers of zirconium boride (ZrB 2 ) 
were formed on quartz substrates at tem- 
peratures of 1,000° to 1,200° C from a 
mixture of ZrCl 4 , BC1 3 , H 2» and Ar ( 145 ). 
Randich synthesized some alloy borides of 
the form (Ti, Zr)B 2 ( 185-186 ). These 
gave Vickers hardness values of approxi- 
mately 3,700 kg mm" 2 for (Ti, Zr)B 2 and 
2,200 kg mm" 2 for ZrB 2 . These alloys 
were prepared by the H 2 reduction of the 
metal chloride and BCI3 ^ n tne tem- 
perature range 800° to 1,100° C, with 
graphite as the substrate. Takahashi 
and Kamiya ( 224 ) studied the system 
Tii_ x Zr x B 2 , where x = 1 to 0. They found 
that increasing the temperature increased 
the deposition rate, but the rate was not 
dependent on total flow rate. The tem- 
perature range was 900° to 1,400° C, and 
dense uniform deposits resulted when the 
metal halide partial pressures were high 
compared with the partial pressure of 
BCI3. 

TITANIUM CARBIDE 

Titanium carbide (TiC) formation tech- 
nology is far more advanced than that for 
TiB 2 . Titanium carbide can be formed by 
the H 2 reduction of TiCl 4 on graphite at 
1,000° to 1,900° C (50) or by the action 
of H 2 on a mixture of TiCl 4 and a suit- 
able hydrocarbon at temperatures ranging 
from 850° to 1,350° C ( 228 , 230 , 233). 
The hydrocarbon can be propane ( 228 , 
233 ), methane (46), isopentane ( 230 ) , and 
ethane, or ethene ( 230 ). Even car- 
bon tetrachloride (CC1 4 ) can be used 
as the source of C (38, 152, 190). 



Toulene ( 138 , 180 ) and benzene ( 139 ) have 
been employed to coat steel as well as 
several hard alloys with TiC. Several 
patents have been granted for processes 
to coat manufactured objects ( 137 ) , gun 
barrels ( 253 ) , and even composite sub- 
strates ( 209 ) . Two patents are concerned 
with codepositing TiC with ductile metals 
such as Co and Ni ( 38 , 253 ) , which is ac- 
complished by introducing CoCl 2 or NiCl 2 
as vapors with a carrier gas such as Ar 
or He. 

Pearce and Marek ( 161 ) have given ex- 
perimental and thermodynamic data to in- 
dicate that C needs to be present to re- 
duce TiCl 4 with H 2 efficiently. This was 
also experimentally verified by Aggour, 
Fitzer, and Schlichting (1). 

There have been several thermodynamic 
equilibrium treatments involving the Ti- 
Cl-H-C system over several temperature 
ranges ( 14 , 43 , 113 , 127 ) . In addition 
to these equilibrium treatments, there 
have been several rate studies reported 
( 107 , 208 , 211 ). Kato, Yasunaga, and 
Tamari reported a growth rate of 1.2 x 
10 cm sec - for TiC grown from the re- 
duction of TiCl 4 and methane with H 2 at 
1,360° C (107). The TiC whiskers grown 
on graphite were in the [111] direction. 
Stjernberg, Gass, and Hintermann ( 208 ) 
have reported that the rate of deposition 
of TiC is proportional to the methane 
concentration and inversely proportional 
to the HC1 concentration at high HC1 con- 
centrations. They used the Langmuir- 
Hinshelwood mechanism to explain their 
experimental data. Subrahmanyam, Lahiri, 
and Abraham ( 211 ) have shown that the ob-> 
served rate of formation of TiC from a 
mixture of TiCl 4 , toluene, and H 2 is 
really a combination of a chemical reac- 
tion rate and a diffusion-controlled 
rate. When large flow rates are used, a 
plot of the logarithm of deposition rate 
versus the reciprocal of the absolute 
temperature produces a linear plot, com- 
pared with low flow rates, which give a 
nonlinear plot. This nonlinearity is due 
to diffusion rates. A thermodynamic 



approach has been published concerning 
the deposition of nonstoichiometric car- 
bides of Ti (245). 

Titanium carbide has been vapor- 
deposited onto cemented carbide sub- 
strates (65, 122 , 210 , 240 ) and onto sin- 
tered hard carbide substrates ( 121 ). In 
one case, the interface between the CVD 
TiC and cemented carbide substrate ( 204 ) 
was examined by scanning electron micros- 
copy as well as Auger electron spectros- 
copy. There was evidence of C loss from 
the substrate during the formation of the 
TiC coating. Lee and Richman ( 122 ) found 
that the presence of air or water in the 
coating system changed the growth rate 
as well as the coating structure be- 
cause of the fine particles of Ti0 2 
that were formed. Karp, Filip, and 
Gibas ( 103 ) found that TiC growth oc- 
curred in the [111] direction on sintered 
carbide substrates. 

The wear resistance of steels has been 
improved by coating with TiC ( 44 , 93 , 
165 ) . There is a review article without 
references by Yamakishi ( 256 ) on the TiC 
treatment of steel, and an article on 
the industrial applications of TiC coat- 
ings on steel ( 166 ) . Several patents 
have been granted (41, 79, JL40, 182 , 
215) that are concerned with the deposi- 
tion of TiC or the apparatus for its 
deposition. 

TiC and TiN coatings reduce fric- 
tion ( 75 , 183 ) or strengthen the sur- 
face ( 202 ) and are also used as decora- 
tive coatings ( 200 ) . Schintlmeister and 
Pacher ( 198-199 ) have discussed several 
of these applications and have predicted 
a great future for these coatings. 
Bonetti (27) has given some hardness val- 
ues as well as thermal expansion coef- 
ficients for TiC on various cemented 
carbide substrates. 

The use of lasers (3_, 131 ) and of plas- 
mas (48-49) for the deposition of TiC has 
been applied with success. The future of 
laser chemical vapor deposition (LCVD) 



seems secure because improved control of 
heating and cooling rates can be obtained 
and cleaner surfaces are exposed to the 
coating process. 

ZIRCONIUM CARBIDE 



Some of the main uses of CVD ZrC are as 
coatings for cutting tools ( 112 , 255 ) and 
for Th0 2 spheres (85) and as reactor fuel 
particles (54, 157 ). 

HAFNIUM CARBIDE 



Zirconium carbide (ZrC) is usually 
formed by the reduction of an appropriate 
zirconium halide with H 2 and a suitable 
hydrocarbon. This can be done at tem- 
peratures of 800° to 1,200° C ( 229 , 236 ). 
Using methane, ZrCl 4 , and H 2 , Tamari and 
Kato ( 236 ) found that ZrC grew preferen- 
tially in the [100] direction with side 
planes generally {l00}. The halide can 
be generated in situ by the action of 
a halogenation agent such as methylene 
chloride upon Zr sponge at 600° C ( 191 ) , 
or it can be obtained by the sublimation 
of ZrCl 4 at 210° to 310° C (235). In one 
method, ZrCl 4 was fed into a fluidized- 
bed reactor as a fine powder (86). Ikawa 
and Iwamoto ( 98 ) employed methyl iodide 
vapor on Zr sponge to produce Zrl 4 . The 
methyl iodide was reacted with the Zr at 
400° to 800° C, and then ZrC was formed 
at temperatures above 1,000° C in a sepa- 
rate reaction zone ( 97 , 99 ) or by addi- 
tion of H 2 at 1,100° C (98). Recently, 
Ikawa (95) produced ZrC by first reacting 
Br 2 with Zr sponge at 600° C and then 
reacting methane and H 2 at approximately 
1,400° C with the ZrBr 4 . The effect of 
the gas composition on the deposition of 
ZrC has been reported ( 156 ) . 

Most of the ZrC obtained by CVD methods 
is produced from ZrCl 4 reacting with H 2 
and methane, as is evidenced by several 
investigations ( 39 , 96 , 184 , 196 , 250 ). 
Samoilenko and Pereselentseva ( 196 ) de- 
posited ZrC on W wire at temperatures of 
1,300° to 1,500° C and obtained good 
growth rates with an activation energy of 
21 kcal mole -1 . Ikawa ( 96 ) found that 
for good ZrC formation both H 2 and the 
hydrocarbon must be present. 

Ambartsumyan and Babich (4) found that 
ZrC formed on graphite by the reaction of 
ZrCl 4 and H 2 obeys the rate equation: 

V = 4.30 x 10 3 exp (-1660/T) um min -1 



Hafnium carbide (HfC) is produced by 
CVD from the chloride or the iodide with 
a H 2 and hydrocarbon mixture. Hertz, 
Spitz, and Besson (70-71) studied the 
conditions for forming HfC from HfCl 4 , 
H 2 , and methane. They found that stoi- 
chiometric HfC could be deposited (70) at 
temperatures of 1,200° to 1,500° C and at 
methane-to-HfCl 4 ratios of 0.25 to 4.5. 
Hertz, Spitz, and Besson (72) have re- 
ported that a maximum deposition rate of 
approximately 350 um hr -1 at 1,500° C 
could be obtained when the H 2 -to-methane 
ratio was approximately 30 and the 
methane-to-HfCl 4 ratio was approximately 
2. The presence of free C lowered the 
coating adherence (71). In general, a 
large excess of H 2 is employed to yield 
hard adhesive coatings (69). At least 
two U.S. patents ( 29 , 62 ) concerning HfC 
have been granted, of which one is for 
coating SiC fibers that are used to re- 
inforce certain composites (62). 

There have been at least five Japanese 
patents (56-58, 77-78) that report the 
preparation of HfC from the action of 
Hfl 4 with a suitable hydrocarbon. In 
these methods, I 2 and Hf are reacted 
first to form Hfl 4 at 200° to 600° C; 
care is required to prevent the decompo- 
sition of the Hfl 4 (57). The hydrocar- 
bon, propane or butane (56), and the Hfl 4 
are then reacted on the substrate at 
temperatures of 800° to 1,250° C (58). 
These patents were for HfC coatings on 
cutting tools. 

TITANIUM CARBONITRIDE 

Since both TiC and TiN offer good cor- 
rosion, abrasion, and erosion protection, 
it would seem that titanium carbonitride 
(TiCxNj.x) might offer better protection. 
With this idea in mind, several inves- 
tigators have studied the carbonitride 
system (40, 172-173, 198). Denker (40) 



studied the mechanical, chemical, and 
electrical properties of monocarbides, 
mononitrides , and monoxides of several 
cubic systems. It was Denker's evalua- 
tion of the materials that predicted the 
carbonitrides would be useful as coating 
materials, particularly for the element 
Ti. 

Titanium carbonitrides are prepared by 
the action of TiCl 4 with H 2 , N 2 , and 
methane at approximately 900° C ( 37 , 195 , 
201 , 206-207 ), Instead of methane, eth- 
ane, propane (25) , chlorobenzene, pyr- 
idine ( 251 ) , or CC1 4 ( 154 ) can be used. 
Takahashi and Itoh ( 219 ) used an ultra- 
sonic field to form carbonitride films 
30 to 120 urn thick. Reactants of propane 
or methane along with H 2 , N 2 , and TiCl 4 
were used to produce the carbonitride 
films. The investigators found the Vick- 
ers microhardness increased from 1,850 to 
3,600 kg mm -2 as x changed from to 1 in 
the formula TiC x Ni_ x . They also found 
that films produced in an ultrasonic 
field were more adherent than those pro- 
duced without it. 

Bitzer and Lohmann (19-20) patented a 
process for preparing diffusion coatings 
at 800° to 1,400° C, using suitable or- 
ganic compounds such as cyanuryl chlo- 
ride, acetonitrile, propionitrile, or 
tetracyanoethylene as the source of C and 
N. In these cases, the substrate was Ti 
or Ti alloy and Ar was the carrier gas 
for the organic compound. Bloom (24) 
employed trimethyl amine along with TiCl 4 
and H 2 at 550° to 750° C to form carboni- 
tride coatings on steel. Yaws and Wake- 
field ( 257 ) have reported on a scaled-up 
system that used the amine and TiCl4 at 
temperatures of 600° to 700° C. 

TITANIUM NITRIDE 

Titanium nitride (TiN) is generally de- 
posited by the action of H 2 and N 2 with 
TiCl4 at temperatures ranging from 700° 
to 1,400° C (2, 104-105 , 216 ). Kato and 
Tamari ( 104 ) studied the crystal growth 
of TiN on graphite, and found the growth 
rate nearly proportional to the square 
root of the H 2 partial pressure. They 
also found the TiN to grow in the [111] 
direction preferentially. High frequency 



discharge conditions have been used 
to obtain TiN as a powder ( 241 ). Peter- 
son ( 168 ) has reported on the role of the 
partial pressure of TiCl 4 in the pro- 
duction of TiN. He found that low 
TiCl 4 partial pressures produced columnar 
grains, whereas higher partial pressures 
resulted in randomly oriented grains. In 
addition, the lower partial pressure re- 
sulted in a faster coating rate. 

One Japanese patent ( 100 ) involves the 
coating of W or Mo alloys with TiN. 
Sadahiro, Cho, and Yamaya ( 194 ) stud- 
ied the effect of temperature and gas 
composition on the deposition of TiN 
onto cemented carbides. Okamoto and 
Umezawa investigated the coating of mild 
steel with TiN, TiC, or Ti ( 158 ). They 
found Vickers hardnesses of 1,600 to 
1,800 kg mm -2 for the TiN coatings and 
1,800 to 3,600 kg mm" 2 for the TiC coat- 
ings. Takahashi and Itoh ( 218 ) obtained 
TiN coatings with Vickers hardnesses of 
1,600 to 2,000 kg mm -2 when the deposi- 
tion was conducted in an ultrasonic 
field. In addition, the film had a 
strong <200> orientation. Some investi- 
gators who studied the growth rate of TiN 
on Mo wire have suggested that the mech- 
anism of growth was surface controlled 
in the early stages ( 142 ) . The linear 
growths were on (100) planes and were 
cubic single crystals. The CVD tempera- 
tures used in this study were between 
1,600° and 2,200° C, with a gas flow 
ratio of 2N 2 to TiCl 4 of 0.7 to 1.0. 

Kagawa ( 101 ) investigated the deposi- 
tion of TiN using TiBr 4 instead of TiCl 4 . 
When N 2 was used as the carrier gas, the 
substrate temperatures needed to be 
greater than 1,260° C, but slightly lower 
temperatures could be employed when a 
mixture of H 2 and N 2 was the carrier gas. 
Bo jar ski, Wokulaska, and Wokulska (26) 
grew TiN whiskers on W substrates by the 
reaction of TiCl 4 with N 2 and H 2 at tem- 
peratures from 1,200° to 1,450° C. The 
crystal growth was found to be in the 
[001] direction with well-formed pyra- 
mid cube tips. 

Some organometallic compounds have been 
utilized with the object of producing 
good deposits at lower temperatures. One 



such compound was the liquid titanium 
tetrakis (dimethylamide) , Ti[N(CH 3 ) 2 ]4 
( 213 ). However, a temperature of 800° C 
was necessary for good TiN formation be- 
cause lower temperatures were not suf- 
ficient for the Ti and N to interact and 
combine. When titanium tetrakis (di- 
ethylamide) was decomposed at 10" 2 torr 
and 350° to 650° C on ceramic substrates, 
a phase that was shown to be Ti(CN) was 
formed ( 120 ) . During the decomposition, 
H 2 , methane, ethane, and ethene were 
formed. The thermal decomposition of 
metal coordination compounds of Ti with 
2,2'-bipyridine (bipy) has been patented 
(34). When 2 and N 2 were introduced 
with the Ti(bipy)3 compound, TiN was said 
to be deposited. The compound was 
sublimed at 250° to 400° C at 10" 4 to 



10" 



torr and then decomposed on the sub- 



strate at about 500° C. Hintermann (74) 
has reported on the coating of bearing 
surfaces with TiC or Ti(CN) for use in 
places where high wear resistance is 
needed. 

Deposition of TiN on steel substrates 
has been accomplished by the action of a 
radio frequency discharge upon a mixture 



of TiCl 4 with N 2 
mixture ( 116 ) . 
850° to 950 { 



or with an N 2 and H 2 
Lower temperatures of 
C could be used. 



ZIRCONIUM AND HAFNIUM NITRIDES 

Zirconium nitride (ZrN) is usually de- 
posited by the CVD process at tempera- 
tures of 950° to 1,300° C from the gas 
mixture of ZrCl 4 , H 2 , and N 2 ( 51 , 141 , 
221 ) . The best conditions were those in 
which the N 2 -to-ZrCl 4 ratio was greater 
than 1 and in which there was at least 
40 mole pet H 2 in the gas mixture (221). 
Whiskers were grown at the higher tem- 
peratures and were usually in the <100> 
orientation ( 141 , 221 ) . If various impu- 
rities are coated on the substrate, 
whisker growth can be improved. The most 
effective impurities are the metals Ni, 
Pd, Pt, Fe, and Mn ( 106 , 144 ). Kato and 
Tamari ( 106 ) found the growth direction 
<100> to generally occur. In a study 
of the kinetics of ZrN formation from 
the gas phase, the reaction rate was 
found to change from first order to zero 
order in ZrCl 4 with increasing ZrCl 4 



concentration, and an activation energy 
of 39 kcal mole -1 was calculated (52). 
There have been at least two thermody- 
namic studies reported ( 114 , 246 ) . 

Hafnium nitride (HfN) can be prepared 
in the same manner as is ZrN, except that 
HfCl 4 is generated in situ by the reac- 
tion of HC1 upon Hf at 700° C (63-64). 
It is quite likely that the lower chlo- 
rides of Hf are also formed ( 64 ) . In ad- 
dition to coating W wires (63) , HfN has 
been used to coat carbide tools for 
machining steel ( 192 ) . 

MISCELLANEOUS COMPOUNDS 

There are several types of compounds 
formed by CVD of the group IVB metals in 
addition to those discussed above, in 
particular the silicides, oxides, and 
sulfides. The production of TiSi or 
TiSi 2 has been achieved by the reaction 
of TiCl 4 with SiCl 4 , using H 2 gas in ex- 
cess ( 117-118 , 153 ) . In most cases , a 
graphite substrate was employed at tem- 
peratures of 900° to 1,300° C. Some 
thermodynamic calculations have been re- 
ported ( 117 ) . One German patent is 
listed ( 59 ) that describes the use of 
lower temperatures in a vacuum apparatus. 
Nickl, Schweitzer, and Luxenberg studied 
the system Ti-Si-C up to temperatures of 
1,200° C using TiCl 4 , SiCl 4 , CC1 4 , and H 2 
( 155 ) . They reported that the ternary 
phases Ti 3 SiC 2 or Ti 5 Si3C x were deposited 
at normal pressures. 

At a temperature of 150° C, thin films 
of Ti0 2 can be produced by the CVD pro- 
cess involving H 2 vapor and tetraisopro- 
pyl titanate ( 53 , 66 ) . Powdered Ti0 2 as 
anatase was produced by the vapor phase 
reaction of 2 with TiCl 4 by Suyama and 
Kato ( 214 ). Thin films of Ti0 2 were pro- 
duced by the vapor pyrolysis of ethyl 
titanate on glass substrates a at a tem- 
perature of 445° C ( 234 ) . Titanium oxy- 
carbide (Ti0 0# 5C 0# 5) was produced by re- 
acting TiCl 4 , H 2 , C0 2 , CO, and methane in 
a reaction tube ( 111 ) . The oxy carbide 
was used to increase cemented carbide 
tool life. Films of Zr0 2 and Hf0 2 were 
prepared by the thermal decomposition of 
Zr or Hf 3~diketonate compounds in the 
gas phase with 2 (13). 



Crystals and whiskers of TiS 2 ( 143 ) and 
ZrS 2 ( 149 ) were produced by the vapor 
deposition of TiCl4 or ZrCl 4 reacting 
with H 2 S on quartz substrates. The nor- 
mal temperature was 400° to 850° C for 
TiS 2 and 800° C for ZrS 2 . In addition, 
Motojima, Takahashi, and Sugiyama (150) 



formed zirconium phosphide (ZrP) whiskers 
at 900° to 1,300° C with a mixture of 
ZrCl 4 , PC1 3 , and H 2 . 

A general summary of some of the reac- 
tions for the preparation of the group 
IVB metal compounds is given in table 1. 



TABLE 1. - Some CVD reactions for group IVB elements 



Reaction 



Vaporization 


Substrate 


temperature, °C 


temperature, 


25- 60 


850-1,400 


200-250 


900-1,300 


25- 60 


850-1,360 


25- 60 


1,200-1,600 


25- 60 


850-1,000 


^lO-SlO 


NAp 


200-250 


800-1,200 


] 600 


NAp 


NAp 


-1,400 


300 


1,200-1,500 


^00-600 


NAp 


NAp 


800-1,250 


25- 60 


-900 


25- 60 


700-1,400 


NAp 


950-1,300 


^00 


NAp 


NAp 


900-1,300 



TiCl^ + 2BC1 3 + 5H 2 * TiB 2 + 10HC1. 



ZrCl 4 + 2BC1 3 + 5H 2 ■*■ ZrB 2 + 10HC1, 



H 2 
TiCl^ + CR\ — ► TiC + 4HC1, 



TiCl 4 + CCI4 + 4H 2 ->• TiC + 8HC1. 



STiCl^ + C 3 H 8 + 2H 2 -► 3TiC + 12HC1, 



Zr + 2CH 2 C1 2 ♦ ZrCl 4 + pyrolysis products, 



H 2 
ZrCl^ + CR\ — ► ZrC + 4HC1, 



Zr + 2Br 2 ♦ ZrBr 4 , 

H 2 

ZrBr 4 + CHt, -* ZrC + 4HBr, 



HfClu + CHl 



H 2 



HfC + 4HC1, 



Hf + 2I 2 ■»■ Hfl 4 

3HfI 1+ + C 3 H 8 ■► 3HfC + 8HI + 2I 2 , 



H 2 
2TiCl 4 + 2CR\ + N 2 — ► 2Ti(CN) + 8HC1, 



2HCI4 + 4H 2 + N 2 + 2TiN + 8HC1, 



2ZrCl 4 + 4H 2 + N 2 -»• 2ZrN + 8HC1, 

2Hf + 2xHCl * 2HfCl x + xH 2 2 ...., 
2HfCl t+ + N 2 + 4H 2 > 2HfN + 8HC1, 



NAp Not applicable. *In situ. 2 Here x = 2, 3, 4. 



GROUP VB METALS [V, Nb(Cb), Ta] 



MISCELLANEOUS VANADIUM COMPOUNDS 

There are few CVD processes for the 
element V in the literature. Vanadium 
carbide (VC) was produced by the gas 
phase reaction of VCI2 with methane at 
1,050° to 1,150° C (47) for the treatment 
of low carbon metal working tools. The 
VC1 2 was usually prepared in situ by 
the action of Cl 2 or HC1 upon V or ferro- 
vanadium ( 162 ) . In addition, Kieffer, 
Fister, and Heidler ( 109 ) deposited a 
titanium-vanadium nitride [(Ti,V)N) coat- 
ing on cemented carbides at 1,100° C, us- 
ing a mixture of TiCl4 , VCI4 , N 2 , and H 2 . 
Fine VN powder was produced by the action 
of VCI4 with NH 3 , H 2 , and N 2 at 700° 
to 1,200° C (80). There is a published 
process to form thin films of V 2 5 by the 
CVD reaction of V0C1 3 with H 2 vapor at 
room temperature ( 134 , 217) . 

NIOBIUM AND TANTALUM BORIDES 

Niobium diboride (NbB 2 ) was prepared by 
the reaction of NbCl 5 and BC1 3 with H 2 at 
temperatures of 950° to 1,200° C (148). 
The NbCl 5 and BC1 3 were prepared in situ 
by the action of Cl 2 on Nb foil and B 4 C 
at 500° and 800° C, respectively (148). 
In e similar manner, Motojima and Sugi- 
yama ( 147 ) deposited TaB 2 on quartz sub- 
strates at temperatures between 900° and 
1,300° C. In this process, TaCl 5 was 
prepared by chlorination of Ta sponge at 
500° C, and BCI3 was prepared from B 4 C at 
800° C. These investigators found that 
the flow rates were low and quite criti- 
cal for diboride formation and that the 
reaction was quite dependent upon the HC1 
concentration. 

Armas (8) conducted a thermodynamic in- 
vestigation to determine if TaB 2 and NbB 2 
could be vapor-deposited in the absence 
of H 2 . By using NbBr 5 or TaRv^ with 
BBr 3 , Armas and Combescure ( 10 ) deposited 
NbB 2 and TaB 2 in the temperature range 
1,000° to 1,700° C at pressures from 10" 2 
to 2 torr. Good hexagonal crystals were 
produced at 1,400° C and a pressure of 



2.5xl0 -2 torr (12) . Armas, Combescure, 
and Trombe ( 11 ) also employed a solar 
furnace to produce similar results. 
Randich ( 187 ) vapor-deposited TaB 2 onto 
several substrates at temperatures of 
500° to 1,000° C, using TaCl 5 and B 2 H 6 
with good success. The coating hardness 
was found to be temperature dependent 
with values around 2,500 kg mm -2 produced 
at temperatures above 600° C. 

NIOBIUM AND TANTALUM CARBIDES 

Niobium carbide (NbC) is generally 
vapor-deposited at temperatures of 900° 
to 1,200° C from the reaction of NbCl 5 
with methane ( 32 , 55). Coatings of NbC 
on steel yielded a hardness of 2,900 kg 
mm -2 when a methane-to-NbCl 5 gas ratio of 
0.5:1 was used ( 136 ) . Hydrogen was 
also used to reduce a mixture of NbCl5 
and CCI4 at temperatures of 1,200° to 
1,600° C ( 129 , 169 ). Several patents 
have been granted for processes that 
react the metal halide with methane ( 135 , 
151 ) or CCI4 ( 242 ). Tantalum carbide 
(TaC) can be prepared by the reduction of 
TaCl 5 and CC1 4 with H 2 at temperatures of 
850° to 1,300° C (242). Takahashi and 
Sugiyama ( 226 ) employed an ac discharge 
to produce TaC from a mixture of TaCl 5 , 
H 2 , and propylene at temperatures of 
400° to 600° C. Thick-wall tubes (up to 
2.5 mm thick) of NbC were deposited on 
graphite tubes using NbCl 5 and methane 
(32) . There was also a continuous CVD 
process reported for coating W filaments 
with TaC (67) . The ac discharge method 
was also employed to produce fibrous 
NbC and NbN at temperatures of 300° to 
700° C, using 
N 2 (231). 



NbCl 5 , H 2 , and propane or 



NIOBIUM AND TANTALUM NITRIDES 

Niobium nitride (NbN) can be prepared 
by the vapor deposition of a mixture of 
NbCl 5 , N 2 , and H 2 at substrate tempera- 
tures of 800° to 1,300° C (110). Recent- 
ly, the growth parameters and crystal 
morphology were investigated (223) . The 



10 



investigators found that a gas mixture 
with an N 2 -to-NbCl 5 ratio greater than 45 
and with an H 2 flow rate of 3.5 mL sec -1 
at 1,350° C produced the single nitride 
phase of NbN. At lower temperatures 
other phases were obtained. The phases 
Nb 2 N and Nb 4 N 3 were also identified 
along with NbN. The NbN crystal growth 
was preferentially in the <111> orienta- 
tion ( 223 ) . Instead of N 2 , NH3 or 
hydrazine can be used to produce Nb 2 N or 
NbN as a fine powder using an H 2 plasma 
source (33) . Use of NbF 5 instead of 
NbCl 5 was shown to produce NbN on a Mo 
substrate at about 900° C ( 193 ). The 
source of nitrogen in this case was N 2 , 
and in addition, a large excess of both 
H 2 and N 2 was needed. 

Tantalum nitride (TaN) was also vapor- 
deposited from the gas phase mixture of 
TaCl 5 , N 2 , and H 2 at temperatures of 700° 
to 1,300° C (73, 222 ). The substrates 
were cemented carbides ( 73 ) and Si ( 222 ) . 
Both Ta 2 N and TaN were found in the 
films produced. The Vickers microhard- 
ness values ranged from 1,200 to 2,200 kg 
mm ( 222 ) . Ammonia has been employed 
as the N source at temperatures of 
700° to 1,300° C at atmospheric pres- 
sure ( 119 ) . The major portion of the TaN 
produced was of the face-centered cubic 
variety. 

Both TaN and NbN were deposited at tem- 
peratures of 300° to 500° C by thermally 
decomposing tantalum or niobium pentakis 
(dimethylamide) ( 213 ) . Use of N 2 or H 2 
as the carrier gas was found to be satis- 
factory. The decomposition product was 



identified as NbN, but the TaN was not 
completely identified. 

MISCELLANEOUS COMPOUNDS 

Several binary Nb superconducting com- 
pounds have been prepared by conven- 
tional CVD. Among these are Nb 3 Ge (30), 
Nb 3 Ga (247), Nb 3 Sn (7, 244 ), and recent- 
ly, Nb 3 Si ( 160 , 254 ). In general, the 
chlorides of Nb and the corresponding 
binary element are produced in situ at 
temperatures of 250° to 350° C (30, 160 ). 
These compounds are not covered in this 
review, as their major use is in the 
electronics industry. Tietjin ( 239 ) has 
published a review that addresses this 
area, and there is also a book by Vossen 
and Werner ( 249 ) concerning the produc- 
tion of thin films. 

The reaction of NbCl 5 with SiCl 4 in 
the presence of H 2 was difficult to con- 
trol ( 160 ) , as generally Nb5Si 3 and me- 
tallic Nb were formed instead of Nb 3 Si. 
Both NbSi 2 and TaSi 2 were deposited 
by the action of NbCl 5 or TaCl 5 with 
SiCl4 and H 2 at temperatures of 700° to 
1,400° C ( 108 ). The disilicides as coat- 
ings were reported to have good oxidation 
resistance properties up to temperatures 
of 1,700° C (108). 

In addition to the compounds mentioned, 
films of Ta 2 05 have been produced for 
semiconductor devices ( 102 ) , as well 
as thin films of LiNb0 3 for optical de- 
vices (36). A summary of the reactions 
and conditions for the group VB metal 
compounds is given in table 2. 



GROUP VIB METALS (Cr, Mo, W) 



CHROMIUM CARBIDE 

The formation of chromium carbide 
(Cr 3 C 2 or CryC 3 ) onto steel is usually 
accomplished by gas chromizing ( 258 ) . 
The steel parts with about 1 pet C are 
treated with CrCl 2 and H 2 at 900° to 
1,000° C, with some methane added to 
aid in the carbide formation (45) . The 
parts can be hardened to Vickers hardness 



values of 3,800 to 4,200 kg mm" 2 . In 
addition to the chromizing process, car- 
bide coatings can be produced by the de- 
composition or pyrolysis of organometal- 
lic compounds of Cr. One such process 
used dicumene chromium at 450° to 650° C 
to produce Cr7C 3 coatings on stainless 
steel turbine blades (60). Another 
process involved the decomposition of 
chromium bis(ethylbenzene) in a vacuum at 



TABLE 2. - Some CVD reactions for group VB elements 



11 



Reaction 



V + 2HC1 -► VC1 2 + H2 1 

VC1 2 + CR h + VC + 2HC1 + H 2 , 



2VCl lt + 2NH 3 + H 2 ■»• 2VN + 8HC1, 



2Nb + 5C1 2 + 2NbCl 5 

B^C + 8C1 2 + 4BC1 3 + CCli, 

2NbCl 5 + 4BC1 3 + 11H 2 ->- 2NbB 2 + 22HC1... 



2Ta + 5C1 2 + 2TaCl 5 

B^C + 8C1 2 -► 4BC1 3 + CC1 4 

2TaCl 5 + 4BC1 3 + 11H 2 > 2TaB 2 + 22HC1... 



2TaCl 5 + 2B 2 H 6 ->• 2TaB 2 + 10HC1 + H 2 , 



2NbCl 5 + 2CH\ + 2NbC + 8HC1 + Cl 2 , 



2NbCl 5 + 2001,+ + 9H 2 -► 2NbC + 18HC1, 



2TaCl 5 + 2001^ + 9H 2 -► 2TaC + 18HC1, 



6NbCl 5 + 7H 2 + 2C 3 H 8 > 6NbC + 30HC1 3 
2NbCl 5 + 5H 2 + N 2 + 2NbN + 10HC1 3 



2NbCl 5 + N 2 + 5H 2 + 2NbN + 10HC1, 



2TaCl 5 + N 2 + 5H 2 ->• 2TaN + 10HC1. 



Vaporization 


Substrate 


temperature, °C 


temperature, 


2 ~900- 


1,000 


NAp 




NAp 


1,050-1,150 




-400 


700-1,200 




2 500 


NAp 




2 800 


NAp 




NAp 


950-1,200 




2 500 


NAp 




2 800 


NAp 


200- 


300 


900-1,300 


200- 


300 


500-1,000 


200- 


300 


900-1,200 


200- 


300 


1,200-1,600 


200- 


300 


850-1,300 


200- 


300 


300- 800 


200- 


300 


300- 800 


200- 


300 


800-2,300 


200- 


300 


700-2,300 



NAp Not applicable. 
The partial pressure of VC1 2 varies directly as P 2 HCl/ p H 7 when both HC1 
and H 2 are present. 
2 In situ. 
3 An ac discharge of 0.05 to 3.0 mA and 60 Hz frequency. 



substrate temperatures 300° to 350° C 
( 126 ) . Some care must be employed to 
prevent deposition of the metal along 
with the metal carbide ( 133 ) . There have 
been several articles that discuss the 
wear-resistant coating of CryC3 on steel 
(90-92) , as well as corrosion-resistant 
Cr7C3 coatings on bearings and some cut- 
ting tools (76, 164). 



MOLYBDENUM CARBIDE 

Molybdenum carbide (Mo 2 C) can best be 
deposited on steel at temperatures of 
400° to 1,000° C by the reaction of MoF 6 
with benzene and H 2 ( 258 ) . Recently, 
Hojo, Tajika, and Kato produced Mo 2 C as a 
fine powder by the reaction of MoCl 4 , H 2 , 
and methane at 800° to 1,400° C (83-84). 



12 



In this process, the MoCl 4 was produced 
in situ at 500° to 600° C from the action 
of Cl 2 on Mo. Films of Mo 2 C can be de- 
posited on glass from the thermal decom- 
position of Mo(C0) fi (248). At a pressure 
of 10" J torr and temperatures of 170° to 
350° C, the deposition rate of M02C was 
increased by using 600-eV electrons at 
3 to 5 mA cm . Microspheres have been 
coated with M02C by the pyrolysis of 
Mo(C0) 6 for use as laser fusion tar- 
gets ( 132 ) . Even an ac discharge method 
has been employed to produce M02C or W 2 C 
from a mixture of isobutane, H 2 , and 
the respective metal chloride at 360° to 
480° C at atmospheric pressure ( 227 ) . 

TUNGSTEN CARBIDE 

There have been more CVD processes de- 
veloped for the production of tungsten 
carbide (WC) than for Mo 2 C. One of the 
earliest methods involved the pyroly- 
sis of W(C0) 6 , at temperatures of 900° 
to 1,100° C, using an inert carrier 
gas (94) . The thermodynamics of the de- 
composition of W(C0)6 has been reported 
by Komorova, Lavrin, and Imris ( 115 ) , who 
used the experimental data of others to 
show that the WC and W 2 C came from the 
decomposition steps and not by a recom- 
bination reaction. Coatings of WC have 
been deposited on different substrates 
such as tools and costume jewelry by 
the reaction of WF 6 with H 2 and a 
suitable hydrocarbon. The hydrocarbon 
can be ethene ( 159 ) , benzene ( 35 , 123 ) , 
toluene ( 6_) , or xylene (6^. At tempera- 
tures up to 550° C, W 2 C can be obtained 
from benzene, toluene, or xylene (6^. 

A mixture of H 2 and CO has also been 
employed with WFs at a temperature of 
925° C and 300 torr (88-89, 238 ). In- 
stead of WF5 , WC16 can De used with H 2 
and methane to form WC coatings on ce- 
mented carbide tool tips ( 243 ) or ultra- 
fine WC powder (81-82). The WC powders 



are produced at temperatures of 1,000° to 
1,400° C (81). Wear-resistant coatings 
of WC were applied to substrates of 
Cu, Cu alloys, and Al ( 259 ) , as well as 
to forms for molds for molding elasto- 
mers ( 181 ) . A controlled nucleation pro- 
cess that gives the surface improved wear 
properties was developed (87) . 

MOLYBDENUM AND TUNGSTEN BORIDES 
AND SILICIDES 

Armas, in addition to depositing the 
borides of Nb and Ta, also studied the 
vapor deposition of Mo and W borides (8- 
10) . Deposition was accomplished by the 
thermal decomposition of a mixture of 
M0CI5 or WCls with BBr3, using con- 
centrated solar radiation as the heat 
source. The borides are of three compo- 
sition types: M 2 B, MB, and M 2 B 5 (M = Mo 
or W). One patent for electrical contact 
layers has reported that Mo and W borides 
were deposited from a mixture of BCI3 and 
H 2 with the respective metal chloride at 
1,800° to 2,000° C (68). The method of 
Armas (8-10) can be used at temperatures 
of 1,400° to 1,600° C, without H 2 ; how- 
ever, BBr3 i s more expensive chan BC1 3 . 

Molybdenum disilicide (MoSi 2 ) has been 
reported as being deposited from a mix- 
ture of M0CI5, SiCl 4 , and H 2 , using Ar to 
control the deposition rate ( 128 ) . The 
deposition of tungsten silicide (WSi 2 ) 
was accomplished by the reaction of WF6 
with SiH 4 at substrate temperatures of 
600° to 800° C ( 124-125 ), and the best 
fine-grained structure was obtained at 
800° C. By carefully controlling the 
ratio of the two flow rates, WSi 2 can be 
formed without the species, W, Si, and 
W 5 Si3. 

A summary of some representative equa- 
tions with conditions for the preparation 
of the group VIB metal compounds is given 
in table 3. 



13 



TABLE 3. - Some CVD reactions for group VIB elements 



Reaction 


Vaporization 
temperature, °C 


Substrate 
temperature, °C 


7Cr[C 6 H 5 CH(CH 3 ) 2 ]2 ♦ c ryC 3 + pyrolysis 


-195 


450- 650 




35- 50 


400-1,000 


Mo + 2C1 2 ■»■ MoCl^ 


1 500-600 

NAp 

25-100 


NAp 


2MOC11+ + CHi* + 2H2 •*■ M02C + 8HC1 


800-1,000 


2Mo(C0)g ■* Mo2 c + 10CO + C0 2 


900-1,000 


2W(C0>6 ■*■ W 2 C + 10CO + C0 2 


-144 


650- 900 


2WF 6 + C 2 H6 + 3H 2 + 2WC + 12HF 


18- 35 
18- 35 


400- 900 


12WF 6 + C 6 H 6 + 33H 2 + 6W 2 C + 72HF 


400- 900 


WF 6 + CO + 4H 2 -► WC + H 2 + 6HF 2 


18- 35 
300 


925 




1,400-1,600 




300 


1,000-1,700 


2WC1 6 + 2BBr 3 ♦ 2WB + 6C1 2 + 3Br 2 3 


140-150 
140-150 


1,400-1,600 




1,000-1,700 


2MoCl 5 + 4SiCli t + 13H 2 + 2MoSi 2 + 26HC1.... 


-160 


700-1,400 


WF 6 + 25111^ ■»■ WSi 2 + 6HF + H 2 


18- 35 


600- 800 







NAp Not applicable. *In situ. 2 Low pressure of 300 torr, 
3 Low pressure of 10~ 2 to 2 torr and use of solar furnace. 



CONCLUSIONS 



Risks of periodic shortages of critical 
and strategic materials continue to exist 
as virtually all of the Western World is 
dependent on imports of critical mineral 
raw materials. Critical materials can be 
conserved through the use of alloys with 
lower strategic metal content and im- 
proved abrasion, erosion, and corrosion 
resistance on the surface. Concentrating 
the critical materials on substrate sur- 
faces by chemical vapor deposition (CVD) 
can provide their needed properties al- 
though the materials are not present in 
the substrates. In addition, synergistic 



effects can result from combining coating 
and substrate properties. Through selec- 
tive use of coatings on low-grade sub- 
strates, it may also be possible to re- 
duce costs while conserving critical 
materials. The thin-film CVD coatings 
that were reviewed have a potential to 
reduce usage of critical materials while 
retaining or improving the desired per- 
formance (resistance to erosion, abra- 
sion, and corrosion) of lower alloy com- 
ponents used in metallurgical, mining, 
and energy conversion systems. 



14 



REFERENCES 



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England, Sept. 21-26, 1975, ed. by J. M. 
Blocher, Jr., H. E. Hintermann, and L. H. 
Hall. Electrochem. Soc, Pennington, 
N.J., 1975, pp. 600-610. 

2. Aivozov, M. I., and V. F. Melek- 
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9. Armas, B. (Study of Chemical 
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1978 (Colloq. Eur. "Surf .-Vide -Me tall. ") , 
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3. Allen, S. D. Laser Chemical Va- 
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4. Ambartsumyan, R. S., and B. N. 
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Graphite Substrate.) Izv. Akad. Nauk 
SSSR, Neorg. Mater., v. 5, No. 2, 1969, 
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5. Archer, N. J. Metallic and Met- 
alloid Coatings From the Gas Phase. 
Chem. Eng. (London), No. 292, December 
1974, pp. 780-782. 

6. Archer, N. J., and K. K. Yee. 
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Coatings Formed at Low Tempera- 
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Reutte, Austria, May 23-26, 1977, ed. 
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8. Armas, B. (Study of Chemical 
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a Vapor Phase. Application to Obtaining 
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28 



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29 



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